Container closure

ABSTRACT

A plastisol composition containing as the resin component a copolymer of a normal α-olefin and maleic anhydride (1:1 mole ratio) having the structure ##STR1## WHEREIN B is a member of the group consisting of ##STR2## and the hydrolysis product thereof, ##STR3## R is H or C x  H 2x+1 , x is 1 to 16 and n is 2-300, and a plasticizer for said resin component. The plastisol when fluxed can be used as a closure gasket for containers.

This is a division of application Ser. No. 756,934 filed Jan. 5, 1977,now U.S. Pat. No. 4,077,935 which is in turn a division of applicationSer. No. 563,018, filed Mar. 28, 1975 and now U.S. Pat. No. 4,020,966.

This invention relates to novel plastisol compositions. Moreparticularly, this invention relates to novel plastisol compositionseminently suitable for various uses including sealing containerclosures.

Conventional plastisol compositions are made up of finely dividedthermoplastic resin particles in a liquid, non-volatile plasticizer inwhich the resin is insoluble at room temperature. On elevating thetemperature of the composition, the resin particles are substantiallycompletely solvated by the plasticizer producing a homogeneous solutionwhich is transformed into a rubbery, thermoplastic gel.

Recently the most widely used resin in plastisol compositions has beenpolyvinyl chloride because of certain inherent characteristics. Vinylchloride resins produced either by bulk, suspension or aqueous emulsionpolymerization or mixtures thereof have been found to be particularlyadvantageous in such compositions. Vinyl chloride resins produced byaqueous emulsion polymerization, because of their excellent stir-inproperties which permit easy dispersion in a liquid plasticizer up to ahigh concentration of the resin at room temperature to form paste likemixtures, have been found particularly useful, especially as gaskets forsealing container closures.

However, vinyl chloride resins whether produced by bulk, suspension orby emulsion polymerization, have certain drawbacks. That is, theemulsion polymerized vinyl chloride due to the necessity of using anemulsifier results in a plastisol which is semi-cloudy in appearance.

Furthermore, the emulsifier is frequently characterized by syneresis,i.e., it exudes from the gelled composition, thereby imparting adisagreeable taste to the food or beverage in which it is in contactwith as a sealant for sealing container closures. In regard tosuspension polymerized vinyl chloride resins, they often contain tracesof suspending agent left over from the polymerization process and saidsuspending agents, like the emulsifier used in emulsion polymerizationtechniques, may later exude or be extracted into foods or beverages. Afurther problem recently noted in regard to polyvinyl chloride is thepossible carcinomatous effect these polymers may have on the human bodydue to possibly residual vinyl chloride monomer being present in thepolymer. In light of the above, there has been a recent search formaterials which can be substituted for polyvinyl chloride in various enduses.

Thus one object of the instant invention is to produce a novel plastisolcomposition. Another object of the instant invention is to produce aplastisol composition which is useful as a sealing gasket in formingclosures on containers. Yet another object of the instant invention isto produce a plastisol composition which on gelling substantiallyminimizes or precludes exuding or extraction of the plasticizer.

The above and other objects are obtained by a plastisol compositioncontaining as the resin component a copolymer of a normal α-olefin andmaleic anhydride (1:1 molar ratio) having the structure ##STR4## whereinB is a member of the group consisting of ##STR5## and the hydrolyzedproduct thereof. ##STR6## R is H or C_(x) H_(2x+1), x is 1 to 16 and nis 2-300, and a plasticizer for said resin component. The maleicanhydride containing copolymer is operable in plastisols in particlesizes ranging from about 0.1 to about 1500 microns, preferably 10 to1000 microns. The plastisol when fluxed can be used as a closure gasketfor containers.

The plastisol of the invention operates in the same method asconventional plastisols. That is herein the term "plastisol" refers todispersions of finely divided thermoplastic resin particles in a liquidnon-volatile plasticizer in which the resin is insoluble or only veryslightly soluble at room temperature. However, at elevated temperaturesthe resin fluxes, i.e. is substantially completely solvated by theplasticizer so that a homogeneous solution is obtained which forms arubbery thermoplastic mass. However, if the plasticizer is such that itreacts with the resin, a thermoset mass is obtained. In addition to theresin and the plasticizer, the formulation may also contain fillers,pigments, stabilizers and various other conventional compoundingingredients.

The plastisol compositions herein are formed by admixture of 100 partsby weight of the copolymer resin with about 65 to 600 parts by weight ofa plasticizer per 100 parts of resin and thereafter heating theplastisol admixture to the melting point of the copolymer resin for atime sufficient to solvate the resin by the plasticizer. Since thesolvation process is time-temperature dependent, it is possible to heatthe plastisol at temperatures below the melting point of the resin forlonger periods of time to obtain a homogeneous solution which will forma rubbery mass. Additionally it is also possible to heat the plastisolcomposition above the melting point of the resin and obtain a fluxedproduct. Thus for example it is possible to heat a plastisol compositionconsisting of 100 parts hexene-1/maleic anhydride copolymer resin(melting range 156°-164° C.) and 100 parts epoxidized soybean oil at atemperature of 106° C. for 18 minutes and obtain a fluxed product. Thesame composition could be heated at 156° C. for 12 minutes or at 200° C.for 2 minutes to obtain a fluxed product.

The basis of all closures for air-tight containers is to hold theclosure firmly against a resilient gasket which seats on the mouth ofthe container.

There are three basic methods of forming gaskets and closures. The firstconsists in depositing a measured amount of liquid gasket-formingcomposition onto the center of a rotating closure whereby thecomposition is distributed over the panel section by centrifugal force.While the rotary method produces gasketed closures rapidly, its use ismainly limited to forming gaskets and closures having a circular shape.

The second method involves a molding technique in which a liquidgasket-forming composition is deposited in the center portion of aclosure cell and the composition is shaped over the panel area by aplunger which may or may not be heated. A third method provides a heateddie having a desired gasket configuration incised on its face. The dieis immersed in a mass of plastisol material whereby the material adheresto the die face and the resultant design from the die to a closure. Thedesign is transferred on the die face may be circular, oval,ellipsoidal, square, triangular, rectangular, etc., and the transferredgasket design conforms to the shape of the closure cell. See U.S. Pat.No. 3,462,331. The novel plastisol composition of the instant inventioncan be used with any of the aforesaid methods for forming gaskets ascontainer closures.

The plasticizer employed in the blend of the invention should be capableof solvating or dissolving the α-olefinmaleic anhydride copolymer resinwhen heated and remain essentially completely compatible with the resinupon cooling. Illustrative plasticizers include, but are not limited to,dialkyl phthalates such as dioctyl phthalate(di-2-ethyl hexyl phthalate)and octyl decyl phthalate, alkyl phthalyl alkyl glycolates, such asethyl phthalyl ethyl glycolate and butyl phthalyl butyl glycolate,dialkyl esters of alkane dicarboxylic acids, such as diisobutyl adipateand dibutyl sebacate, acetyl trialkyl citrates, such as acetyl tributylcitrate and trialkyl and triaryl phosphates, such as trioctyl phosphateand tricresyl phosphate. Other useful plasticizers include alkyl estersof fatty acids such as octyl stearate; epoxidized triglycerides such asepoxidized soybean oil and polymeric polyester plasticizers such aspolymeric glycol adipate. Additionally plasticizers such as polyestersderived from dibasic acids and glycols may also be used. Examples ofsuch type include but are not limited to dipropylene glycol dibenzoate,diethylene glycol dibenzoate, triethylene glycol dibenzoate,polyethylene glycol 200 dibenzoate, polyethylene glycol 600 dibenzoate,and the like. Additionally glycols per se such as polyethylene glycolhaving a molecular weight of about 600 can also be employed as theplasticizer in the instant composition. Mixtures of the aforesaidplasticizers are also operable.

The amount of plasticizer employed can range between about 65 to about600, preferably 80 to 200 parts by weight per hundred parts by weight ofthe resin component.

If desired, it is also possible to include thickening agents in theplastisol composition. Said thickening agents prevent packing of theresin component over extended periods of time. Siliceous thickeningagents are suitable herein and contain at least one silicon-oxygen bondexemplified by such materials as the alkaline metal silicates, e.g.,sodium silicate, alkaline earth metal silicates, e.g., calcium silicate,talc, etc. Colloidal silica can also be used as the thickening agent inthe composition of the instant invention. Thickening agents are usuallyadded in amounts ranging from 0.10 to 5 weight percent of the resin andplasticizer components.

Other conventional additives may be included in the composition of theinvention in amounts, e.g. up to about 70 weight percent provided thatsuch additives do not deleteriously affect the characteristics of thecomposition. Examples of such materials are fillers such as wood flourand diatomaceous earth; stabilizers such as tetrasodium pyrophosphate,tribasic lead silicate, calcium stearate, zinc stearate, dibasic leadstearate, organo-tin complexes; pigments such as carbon black, titaniumdioxide, and aluminum powder; and dispersing agents such as zincresinate, lecithin, glycol stearate, propylene glycol laurate andglycerol monooleate.

Furthermore, the plastisols of the instant invention can be puffed orfoamed using water or conventional foaming methods and blowing agents.Examples of suitable blowing agents for use herein, include but are notlimited to, azo compounds such as azobisisobutyronitrile anddiazoaminobenzene; N-nitroso -compounds such asN,N'-di-methyl-N,N'-dinitroso-terephthalamide; sulfonyl hydrazides suchas 4,4'-oxybiz(benzenesulfonyl hydrazide) and the like. Good cellformation together with an impervious surface are realized when 0.2 to5.0% based on the weight of the resin of a blowing agent or mixturesthereof is used in the plastisol formulation.

In practicing the instant invention it is not only possible to formthermoplastic compositions on heating and subsequent cooling but also toform thermoset compositions. That is, by proper selection of theplasticizer or other additive, reactions with the anhydride or acidfunctionality on the copolymer resin result in a thermoset material.

Compositions comprising the alpha-olefin/maleic anhydride copolymers ofthis invention can be converted to apparently or actually crosslinkedproducts insoluble in many common solvents and infusible at considerablyelevated temperatures. One means of preparing such cross-linkedmaterials is to admix in the composition certain free metallic cationsselected mainly from Groups I, II, III and VIII of the Periodic Table ofthe elements. The exact nature of the forces leading to crosslinking isnot understood at this time. There is reason to believe, however, thatstrong ionic interchain forces play the major role in controllingproperties of the final admixed and fluxed compositions. These ionicforces are developed between ionized carboxyl groups derived from thependant anhydride or acid moieties and the free metallic cations,similar to forces postulated for somewhat similar copolymers describedin Fr. No. 1,393,730. Ionizable metallic compounds useful for makingionically reinforced compositions of this type are selected from GroupI, II, III, or VIII of the Periodic Table.

Another means of crosslinking the copolymer compositions of thisinvention is to use covalent chemical bonding techniques. This isaccomplished in one instance by interacting the pendant anhydride and/orcarboxylic acid groups with appropriate compounds that contain two ormore reactive hydrogen containing functional groups. These compounds inessence are considered herein as reactive plasticizers, i.e., they servethe function as plasticizers until the plastisol is fluxed, at whichtime they are partially or completely chemically bound to the resinpolymer backbone. These compounds can be used alone with the resin or incombination with non-reactive plasticizers. Compounds of this typeinclude but are not limited to polyols; polyamines; polythiols; etc. Inanother instance the pendant anhydride and/or carboxylic acid groups arereacted with other reactive species exemplified by but not limited topolyisocyanates, polyepoxides, polyhydrazides, hydroxyamines,hydroxythiols, aminothiols, hydroxyepoxides and the like. Thus herein itis possible to select a plasticizer containing di- or polyamine, epoxy,isocyanate or hydroxy groups therein which on heating results in athermoset material. For example, a plasticizer such as tetraethylenepentamine reacts with the anhydride groups on the copolymer resin toyield an acid and a half amide of the anhydride on heating which yieldsa thermoset product. The same is true for an epoxy containing compoundsuch as epoxidized soybean oil which will react with the anhydride groupof the copolymer resin and result in a thermoset material. A furtherexample of the formation of such a thermoset material would be thereaction between a plasticizer such as polyethylene glycol wherein thehydroxyl groups on the polyethylene glycol will react with the anhydrideto yield the half ester of the anhydride and result in a thermosetmaterial. Thus the anhydride copolymer resin herein may be crosslinkedby reaction with various polyfunctional hydroxy, amine and epoxycontaining compounds as will be shown by examples hereinafter. A furthermethod of accomplishing crosslinking herein is by heating the anhydrideor acid containing copolymer resin with a crosslinking or anon-crosslinking plasticizer and certain ionizable metallic compoundswherein the metal is selected from Groups I, II, III and VIII of thePeriodic Table such as calcium oxide, magnesium oxide, sodium carbonate,barium oxide, strontium oxide, zinc oxide and aluminum oxide. Theseionizable metallic compounds are added to the plastisol composition inan amount ranging from about 0.5 to 50 parts per 100 parts copolymerresin.

A cross-sectional view of a crown closure containing a fluxed vinylresin plastisol liner of this invention is shown in the accompanyingdrawing.

Referring to the FIGURE, the crown shell which is shown inverted has acircular top portion 1 and a crimped skirt portion 2 joined by asmoothly curved top corner edge 3. The interior of the shell has anoverall lacquer coating 4. Superimposed on the lacquer coating andadhered thereto is the resin plastisol of the instant invention as asealing liner which has a thin central portion 5 and a substantiallythicker annular sealing portion 6.

The following examples are set forth herein to explain, but expresslynot limit, the instant invention. Unless otherwise noted, all parts andpercentages are by weight.

EXAMPLE I

Several plastisol compositions were formulated using various amounts andkinds of commercially available alpha-olefin and maleic anhydridecopolymer resins having a particle size of minus 500 microns. Thecompositions after being homogeneously admixed were placed in a forcedair oven for 10 minutes at 200° C. Various of the resultant solidified,fluxed products were measured for Shore A Hardness. The compositions aredesignated A-N and are listed in Table I.

In all cases the compositions before heating, had a good rheology, i.e.a fluid, slightly pasty composition which flowed through an orificeunder pressure without a tendency to plug, i.e. filter the plasticizerout of the composition. Furthermore compositions H-M indicated they werethermoset materials since on being reheated, after fluxing and cooling,they failed to flow. The Shore A Hardness data of compositions A-H ofthe instant invention indicate the flexibility of the plastisolcompositions which can be obtained. Thus, one can formulate plastisolcompositions of the instant invention over a wide range to obtain theproperties desired for a particular end use.

                                      TABLE I                                     __________________________________________________________________________    Composition,parts by weight                                                                 A B C  D E F G H.sup.(6)                                                                        I.sup.(6)                                                                       J.sup.(6)                                                                       K.sup.(6)                                                                        L.sup.(6)                                                                        M.sup.(6)                                                                        N.sup.(6)                                                                        O.sup.(6)                     __________________________________________________________________________    ethylene/maleic anhydride                                                     copolymer.sup.(1)                            10                               ethylene/maleic acid                                                          copolymer.sup.(2)                               10                            hexene-1/maleic anhydride                                                     copolymer.sup.(3)                                                                           20                                                                              20                                                                              20 20    20                                                                              20 10                                                                              10                                                                              10 10 10                                  octadecene-1/maleic                                                           anhydride copolymer.sup.(4)                                                                          20                                                                              20                                                   dipropylene glycol                                                            dibenzoate    14                                                                              20                                                                              10 17                                                                              14                                                                              20                                                   epoxidized soybean oil                       10 10                            polyethylene glycol.sup.(5)                                                                              20                                                                              20                                               tetraethylene pentamine         10                                            dioctyl phthalate                 14                                                                              14 14 14                                  ZnO                                  5                                        CaO                          0.1   5                                          Al.sub.2 O.sub.3                        5                                     Na.sub.2 CO.sub.3                          5                                  Shore A Hardness on                                                           Cooling       97                                                                              73                                                                              100                                                                              82                                                                              31                                                                              13                                                                              54                                                                              84                                               __________________________________________________________________________     .sup.(1) Melting Pt. 235° C; Equivalent acid value 890; M Wgt.         30,000                                                                        .sup.(2) Melting Pt. 217° C; Equivalent acid value 890                 .sup.(3) Melting Range 156-164° C; Equivalent acid value 617           .sup.(4) Melting Range 115-119° C; Equivalent acid value 321; M        Wgt. 20,000                                                                   .sup.(5) Molecular wgt. 600                                                   .sup.(6) After fluxing and cooling, product returned to oven at               250° C for 20 minutes. Lack of flow indicates thermoset material. 

The following example shows the use of the composition of the instantinvention in forming a sealing gasket in a closure.

EXAMPLE II

The following plastisol composition was admixed in a tray untilhomogeneous:

45 parts commercially available hexene-1/maleic anhydride copolymer(minus 500 microns particle size; molecular weight 30,000)

27.5 parts commercially available polypropylene glycol - molecularweight 425

27.5 parts epoxidized soybean oil

A heated cylindrical die face provided with a peripheral channel adaptedto form a gasket having an annular ring integral with a thin centerportion was immersed in the tank containing the plastisol to a depthsufficient to fill the peripheral channel with plastisol with aconcommitant pick-up of a thin center portion, i.e., 180-250 milligramsplastisol. The heat from the die caused that portion of the plastisol incontact with the die face to partially flux and adhere to the die. Thedie and the adhered plastisol were then transferred to a closure shellof tin-free steel with a protective coating of vinyl resin lacqueredthereon. The shell is situated in a single station arbor press. The dieis held in the shell for a period of 1.5-6 seconds at a temperatureranging from 275°-375° F. and a pressure of 150-200 psi. The die isremoved and the shell with the partially fluxed plastisol was post bakedfor 50 seconds at 390° F. in a forced air oven to convert the partiallyformed gasket to a solidified, cohesive form. The resultant gasket was aresilient cohesive mass which was able to withstand standard carbonationtests.

EXAMPLE III

A plastisol composition was made up by admixing 50 parts by weight ofcommercially available hexene-1/maleic anhydride copolymer resin (-500microns) having a melting point range of 156°-164° C. and 50 parts byweight of commercially available polyoxypropylene glycol having amolecular weight of about 425 until the mixture was homogeneous. Using a#3 Meyer bar, the following articles were coated with the plastisolmixture:

(a) cotton jersey

(b) vinyl asbestos floor tile

(c) a piece of white pine wood

(d) concrete block

(e) polyester terephthalate film "Mylar"

(f) aluminum sheet

(g) glass

(h) ceramic tile.

The coated articles were then heated at a temperature between 175°-200°C. in a forced air oven for 10 minutes. On removal it was noted that aclear, continuous, adhesive coating of the plastisol resulted on each ofthe various sutstrates.

The following examples in Table II show the operability of the copolymerof the instant invention to form a plastisol with various plasticizers.In all examples in Table II, 100 parts by weight of commerciallyavailable hexene-1/maleic anhydride copolymer (-500 microns) were usedas the resin. The plastisols were all heated at 200° C. for 10 minutesin a forced air oven. The Shore A Hardness was measured after coolingthe fluxed product to room temperature.

                                      TABLE II                                    __________________________________________________________________________    Plasticizers                                                                                                        Parts by                                Type                                  Weight                                                                             Shore A Hardness                   __________________________________________________________________________    I.  Unreactive Plasticizers                                                   Dibutyl phthalate                     100  45                                 Dioctyl azelate                        80  20                                 Butyl benzyl phthalate                 90  70                                 n-Octyl decyl phthalate               100  50                                 Tetralin                              100  90                                 Trimethylolpropane triacrylate         80  >90                                Ditridecyl phthalate                  100  11                                 II.  Reactive Plasticizers                                                    Epoxidized Soybean oil                150  80                                 Octyl epoxy tallate                   100  90                                 Polypropylene glycol 425              100  65                                 Polyethylene glycol 600               100  62                                 Polyethylene glycol 200               100  12                                 Ethylene glycol                       100   8                                 Diethylene glycol                     100  29                                 Dipropylene glycol                    100  27                                 A polyether polyol having a mole weight of 1000; hydroxyl no. of                                                    100.5;                                                                             70                                 commercially available from Union Carbide under the tradename "Niax           LG-168"                                                                       A bisphenol A based epoxy liquid resin commercially available                                                       615m 15                                 Dow Chemical Co. under the tradename "Epoxy DER 331"                          An epichlorohydrin/bisphenol A type liquid epoxy resin commercially           avail-                                300  82                                 able from Dow Chemical Co. under the tradename "Epoxy DER 317"                A low molecular weight epichlorohydrin/bisphenol A-type liquid epoxy          resin                                 400  49                                 commercially available from Shell Chemical Co. under the tradename            "Epoxy EPON 828"                                                              A epichlorohydrin/bisphenol A-type liquid epoxy resin commercially                                                  300il-                                                                             34                                 able from Shell Chemical Co. under the tradename "Epoxy EPON 825"             A mixture of branched di- and tri-epoxides made by the condensation                                                 300  72                                 epichlorohydrin and glycerine having an epoxide functionality of 2.2,         commercially available from Shell Chemical Co. under the tradename            "Epoxy EPON 812"                                                              A dicyclodiepoxy carboxylate commercially available from Union                                                      200bide                                                                            89                                 under the tradename "UNOX 201"                                                Dipropylene glycol                     65  88                                 __________________________________________________________________________

EXAMPLE IV

The following examples in Table III show the operability of theplastisol composition of the instant invention with various fillers. Inall examples 100 parts by weight of commercially availablehexene-1/maleic anhydride copolymer resin (-500 microns) were admixedwith commercially available epoxidized soybean oil in varying amountsalong with the various fillers shown in Table III. The resultantplastisol was heated at 200° C. in a forced air oven for 10 minutes.After cooling the Shore A hardness was measured on the fluxed,solidified, cured product.

                  TABLE III                                                       ______________________________________                                                                              Shore A                                 Epoxidized Soybean Oil                                                                      CaCO.sub.3                                                                            Talc   "Cab-o-sil".sup.(1)                                                                    Hardness                                ______________________________________                                        300                   300             62                                      330                   270             65                                      360                   240             69                                      390                   210             78                                      420                   180             82                                      450                   150             86                                      300           300                     68                                      330           270                     70                                      360           240                     71                                      390           210                     78                                      420           180                     84                                      450           150                     87                                      575           100            30       50                                      ______________________________________                                         .sup.(1) Colloidal silica commercially available from Cabot Corp.        

EXAMPLE V

The following examples in Table IV show various plastisol compositionswherein admixtures of various plasticizers with or without fillers wereformed. In all the examples in Table IV, 100 parts by weight ofcommercially available hexene-1/maleic anhydride copolymer resin (-500microns) were admixed with varying amounts of epoxidized soybean oil andother plasticizers with or without fillers as set forth in Table IV. Theadmixed plastisols were fluxed in a forced air oven at 200° C. for 10minutes. The Shore A hardness was measured after cooling.

                  TABLE VI                                                        ______________________________________                                        Mixtures of Epoxidized                                                        Soybean Oil with Other Plasticizers (100 parts hexene-1/                      maleic anhydride copolymer)                                                                                          Hard-                                  Soybean Oil                                                                            Other (parts)    Talc   CaCO.sub.3                                                                          ness                                   ______________________________________                                        70       Dioctyl adipate (30)          90                                     70       Light Mineral Oil (30)        73                                     70       Trioctyl trimellitate (30)    82                                     70       Diisodecyl phthalate (30)     86                                     70       Dioctyl isophthalate (30)     90                                     80       Dioctyl phthalate (20)        90                                     60       Dioctyl phthalate (40)        90                                     40       Dioctyl phthalate (60)        80                                     20       Dioctyl phthalate (80)        51                                     150      Dioctyl phthalate (150)                                                                        100          41                                     165      Dioctyl phthalate (165)                                                                        82           42                                     1809     Dioctyl phthalate (180)                                                                        66           49                                     195      Dioctyl phthalate (195)                                                                        54           61                                     210      Dioctyl phthalate (210)                                                                        43           75                                     225      Dioctyl phthalate (225)                                                                        33           77                                     150      Dioctyl phthalate (150) 100   40                                     165      Dioctyl phthalate (165) 82    50                                     180      Dioctyl phthalate (180) 66    60                                     195      Dioctyl phthalate (195) 54    62                                     210      Dioctyl phthalate (210) 43    73                                     225      Dioctyl phthalate (225) 33    76                                     ______________________________________                                    

EXAMPLE VI

The following examples in Table V set forth various copolymer resinsoperable in the plastisol composition of the instant invention. In allexamples, 100 parts by weight of the commercially available copolymerresin were admixed with varying amounts of the plasticizers set forth inthe table and then fluxed in a forced air oven at 200° C. during a 10minute period. The Shore A hardness of the fluxed, solidified plastisolwas measured after cooling.

                                      TABLE                                       __________________________________________________________________________    Resin.sup.(1)      Plasticizer (Parts)       Hardness                         __________________________________________________________________________    Decene-1/maleic anhydride copolymer                                                              Epoxidized Soybean Oil (100)                                                                            49                               Tetradecene-1/maleic anhydride                                                                   Epoxidized Soybean Oil (100)                                                                            32                               copolymer                                                                     Octadecene-1/maleic anhydride                                                                    Epoxidized Soybean Oil (100)                                                                            20                               copolymer                                                                     Octadecene-1/maleic anhydride                                                                    A bisphenol A based epoxy liquid resin                                                                  42mmercially                     copolymer          available from Dow Chemical Co. under the trade-                              name "Epoxy DER 331"](300)                                 Octadecene-1/maleic anhydride                                                                    An epichlorohydrin/bisphenol A type liquid                                                              36oxy                            copolymer          resin commercially available from Dow Chemical                                Co. under the tradename "Epoxy DER 317" (300)              Octadecene-1/maleic anhydride                                                                    A low molecular weight epichlorohydrin/bisphenol                                                        47                               copolymer          A - type liquid epoxy resin commercially avail-                               able from Shell Chemical Co. under the trade-                                 name "Epoxy EPON 828"](300)                                Octadecene-1/maleic anhydride                                                                    Epichlorohydrin/bisphenol A-type liquid epoxy                                                           62sin                            copolymer          commercially available from Shell Chemical Co.                                under the tradename "Epoxy EPON 825"](300)                 Octadecene-1/maleic anhydride                                                                    A mixture of branched di- and tri-epoxides made                                                         13                               copolymer          condensation of epichlorohydrin and glycerine                                 having an epoxide functionality of 2.2, commer-                               cially available from Shell Chemical Co. under                                the tradename "Epoxy EPON 812" (200)                       Octacecene-1/maleic anhydride                                                                    A dicyclodiepoxy carboxylate commercially                                                               46ailable                        copolymer          from Union Carbide under the tradename "UNOX 201"                             (200)                                                      __________________________________________________________________________     .sup.(1) 100 parts by weight                                             

EXAMPLE VII

To show the bondinbg ability of the plastisols of the instant invention,100 parts by weight of a commercially available hexene-1/maleicanhydride copolymer resin (-500 microns) were admixed with variousplasticizers, applied between various metal plates and pressed on aplaten press at 160° C. for 10 minutes to bond the plates together. Thethus bonded plates were then measured at 23°±1° C. and 50% RH for lapshear in accord with the procedure set out at ASTM 1002-64 on an InstronTensile tester at a rate of strain of 1 inch/minute. The results are setforth in Table VI.

                                      TABLE VI                                    __________________________________________________________________________    Plasticizer                                                                                       Parts by     Lap Shear                                    Type                Weight                                                                             Adhering Metal                                                                        lbs./in..sup.2                               __________________________________________________________________________    A low molecular weight epichlorohydrin/                                                           75   Black Plate                                                                           467.5                                        bisphenol A-type liquid epoxy resin com-                                      mercially available from Shell Chemical                                       Co. under the tradename "Epoxy EPON 828"                                      A low molecular weight epichlorohydrin/                                                           75   Tin Plate                                                                             390.5                                        bisphenol A-type liquid epoxy resin com-                                      mercially available from Shell Chemical                                       Co. under the tradename "Epoxy EPON 828"                                      A low molecular weight epichlorohydrin/                                                           75   Tin Free Steel                                                                        238                                          bisphenol A-type liquid epoxy resin com-                                      mercially available from Shell Chemical                                       Co. under the tradename "Epoxy EPON 828"                                      Polypropylene glycol-425                                                                          100  Tin Plate                                                                             301.5                                        Polypropylene glycol-425                                                                          100  Black Plate                                                                           326                                          Polypropylene glycol-425                                                                          100  Tin Free Steel                                                                        505.5                                        __________________________________________________________________________

EXAMPLE VIII

A plastic cap closure having a I. Dia of 21/2 inch was placed flat-sidedown and another plastic cap closure having an O. Dia of 13/4 inch wasinserted therein concentrically. The annulus between the plastic capclosures was filled to a depth of about 1/4 inch with a plastisolcomposition consisting of 100 parts by weight of a commerciallyavailable hexene-1/maleic anhydride copolymer resin having a particlesize of -500 microns and a molecular weight of about 30,000 and 100parts by weight of commercially available propylene glycol having amolecular weight of 425. A glass cylinder, 3 inches high, having an I.Dia of 1 15/16 inch and an O. Dia of 2 15/16 inches was pressed into theplastisol in the annulus and the thus formed element was thereafterplaced in a forced air oven for 10 minutes at 160° C. to flux theplastisol and form a sealant therewith. The element was removed from theoven and cooled to room temperature. The lower sealed portion of theglass cylinder was placed in a water bath to determine whether or notwater would escape through the sealant into the central portion of theglass cylinder. No water passed through the sealant into the centralportion of the glass cylinder during a 24 hour period.

EXAMPLE IX

A plastisol composition consisting of an admixture of 10 parts by weightof commercially available hexene-1/maleic anhydride copolymer resin(-500 microns) and 10 parts by weight of commercially availablepolypropylene glycol having a molecular weight of 425 was charged to a 2inches circular mold having a height of 1/4 inch which had previoulsybeen sprayed with a silicon release agent. The mold was placed in aforced air oven for 10 minutes at 200° C. A solid, homogeneous mass inthe shape of the mold was removed from the mold.

The plastisol composition of the instant invention has many and varieduses. Such uses include but are not limited to, a material for use asgaskets, closures, decorative and protective coatings, caulks,architectural and automotive sealants, adhesives, mastics, thermosettingor thermoplastic fiber reinforced composites, impregnants, binders,sizes, printing plates, photoresists, lacquers, potting andencapsulation compounds, side seam cements, shaped molded articles andthe like.

What is claimed is:
 1. A container closure comprising a cap havingdeposited therein a resinous mass functioning as a gasket to seal thecontainer when the closure is in sealing relationship with thecontainer, said resinous mass comprising a fluxed plastisol of acomposition comprising (a) a copolymer resin of a normal α-olefin andmaleic anhydride (1:1 mole ratio) having a particle size in the range offrom about 0.1 to about 1500 microns and having the structure ##STR7##wherein B is a member of the group consisting of ##STR8## R is H orC_(x) H_(2x+1), x is 1 to 16 and n is 2-300, and (b) about 65 to 600parts by weight of a polyester plasticizer per 100 parts by weight ofthe copolymer resin.
 2. The container closure of claim 1 including anionizable metallic compound wherein the metal is selected from Group I,II, III or VIII of the Periodic Table.